JP2003005329A - Processing agent composition for silver halide photographic sensitive material, color developing solution, bleaching solution, bleach fixing solution, stabilizing solution, fixing solution, amplifier solution and black-and-white developing solution - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photographic processing agent composition giving a stable processing solution free of precipitation and sludge generation due to the presence of metal ions, capable of stable processing over a long period of time without clogging an attached filter when processing is carried out with an automatic processing machine and excellent in biodegradability and suitable for the protection of the global environment and to provide a color developing solution, a bleaching solution, a bleach fixing solution, a stabilizing solution, a fixing solution, an amplifier solution and a black-and-white developing solution. SOLUTION: The processing agent composition for a silver halide photographic sensitive material contains a compound of formula [A].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic processing composition for processing an exposed silver halide photographic light-sensitive material, and more particularly to a photographic processing composition for blocking harmful metal ions. As a silver halide light-sensitive material containing a novel chelating agent as a photographic processing composition, a color developing solution, a bleaching solution, a bleach-fixing solution, a stabilizing solution, a fixing solution, an amplifier solution and a black-and-white developing solution Is.

[0002]

2. Description of the Related Art Generally, in order to obtain an image by processing an exposed silver halide photographic light-sensitive material (hereinafter, also simply referred to as a photographic light-sensitive material, a light-sensitive material or a light-sensitive material), a developer or a fixer is used. As a result, treatment with various treatment liquids is required. More processing steps are required, especially for obtaining color images. Since the treatment liquid used for these treatments contains many components, if the water used for the preparation contains metal ions such as calcium, magnesium and iron, it reacts with them to cause precipitation or precipitation. This produces sludge. Further, there are drawbacks such as clogging of the filter attached to the automatic development processor or adhesion to the surface of the photographic light-sensitive material being processed to cause contamination.

Even when pure water is used to prevent this when preparing a processing solution, metal ions may be eluted from the photographic light-sensitive material into the processing solution, or metal ions may be brought in from the previous processing step. However, it was extremely difficult to completely prevent the precipitation and sludge generation in the treatment liquid.

Furthermore, some of the various components contained in the treatment liquid lose their effectiveness because their oxidation and decomposition are promoted by the action of metal ions.
There are drawbacks such as generation of fog and reduction of photosensitivity.

In order to prevent these undesired effects of metal ions on the processing solution, a so-called chelating agent for sequestering metal ions is used as a processing agent composition for silver halide photographic light-sensitive materials (hereinafter simply referred to as photographic processing agent composition). (Also referred to as ")" is proposed and put into practical use. For example, a polyphosphate such as sodium hexametaphosphate proposed by British Patent No. 520,593, an alkylidene diphosphonic acid proposed by US Pat. No. 321,445, proposed by No. 3,201,246. Examples thereof include aminopolymethylenephosphonic acid and aminopolycarboxylic acid represented by ethylenediaminetetraacetic acid.

However, even when these chelating agents are blended, there are various drawbacks in practical use, and it is the actual situation that they cannot be satisfied.

That is, since polyphosphate has a small sequestering power for metal ions and is particularly weak against heavy metal ions, it cannot be put to practical use. Alkylidene diphosphonic acid has a problem that when a calcium ion and a sodium ion coexist at a certain concentration or more, a solid precipitate is generated to cause a trouble in the automatic processor. Ordinary aminopolycarboxylic acids represented by ethylenediaminetetraacetic acid and aminopolymethylenephosphonic acids represented by aminotrimethylenephosphonic acid have excellent sequestering power, but a color developer containing hydroxylamine. Then, there is a disadvantage that hydroxylamine is decomposed in the presence of metal ions and fog occurs when processed with this developing solution, and in a black and white developing solution, oxidation of the developing agent is promoted to deteriorate storage stability,
It has the drawback of causing significant fog on high speed films.

Furthermore, in the bleaching solution, a ferric acid complex salt of an organic acid is usually used as a bleaching agent, and a chelating agent is used as a stabilizer thereof, but a chelate having a higher stability to ferric ion than the organic acid. If a chelating agent is added, ferric ions are taken in and the bleaching ability is impaired, and if a chelating agent is not added, there is a problem that the complex itself becomes unstable and iron hydroxide precipitates. The choice was desired.

Thiosulfate is often used as a fixing agent in bleach-fixing solutions and fixing solutions, but there is a problem that it becomes unstable and easily sulfides due to heavy metal ions contained in dissolved water. (EDT
The chelating agent such as A) has a problem of promoting sulfide.

The stabilizing solution also has a problem that scum is generated due to heavy metal ions contained in the dissolved water, which cannot be suppressed by a chelating agent such as EDTA.

In the amplifier solution, hydrogen peroxide and cobalt hexamine complex are usually used for the purpose of amplification, but there is a problem that hydrogen peroxide and cobalt hexamine complex become unstable due to heavy metal ions contained in the dissolved water. However, if EDTA is used to suppress them, it will worsen.

As described above, all of the conventionally proposed chelating agents have some drawbacks, and in reality, they are not sufficiently effective when used in a photographic processing composition.

Further, in recent years, due to social and environmental requirements such as low pollution and economic requirements such as cost reduction, the replenishment amount of the photographic processing liquid tends to be reduced more and more. The accumulated amount of metal ions such as calcium also tends to increase.

Further, in recent years, from the standpoint of protecting the global environment, it has been desired to use a material having good biodegradability, and there are even moves to restrict use in some areas.

[0015]

SUMMARY OF THE INVENTION The present invention has been made to solve these problems, and the first object is to obtain a stable treatment liquid free from precipitation or sludge generation due to the presence of metal ions. A processing composition for a silver halide photographic light-sensitive material, a color developer, a bleaching solution, a bleach-fixing solution, a stabilizing solution,
To provide a fixing solution, an amplifier solution, and a black and white developing solution.

The second purpose is to provide a processing agent composition for a silver halide photographic light-sensitive material which can be stably processed for a long period of time when it is processed by an automatic development processor and does not cause clogging of an attached filter. The object is to provide a product, a color developing solution, a bleaching solution, a bleach-fixing solution, a stabilizing solution, a fixing solution, an amplifier solution, and a black-and-white developing solution.

A third object is a processing agent composition for silver halide photographic light-sensitive materials, which has excellent biodegradability and is suitable for protecting the global environment, a color developing solution, a bleaching solution, a bleach-fixing solution, a stabilizing solution and a fixing agent. Solution, an amplifier solution, and a black-and-white developing solution.

[0018]

The above object of the present invention can be achieved by the following constitutions.

1. A processing agent composition for a silver halide photographic light-sensitive material, comprising a compound represented by the above general formula [A].

2. A color developing solution for a silver halide photographic light-sensitive material, comprising a compound represented by the above general formula [A].

3. A bleaching solution for a silver halide photographic light-sensitive material, which contains a compound represented by the general formula [A].

4. A bleach-fixing solution for silver halide photographic light-sensitive materials, which contains the compound represented by the general formula [A].

5. A stabilizing solution for a silver halide photographic light-sensitive material, comprising a compound represented by the above general formula [A].

6. A fixing solution for a silver halide photographic light-sensitive material, comprising a compound represented by the general formula [A].

7. An amplifier liquid for a silver halide photographic light-sensitive material, which contains a compound represented by the above general formula [A].

8. A black-and-white developing solution for a silver halide photographic light-sensitive material, which contains a compound represented by the general formula [A].

9. 2. The processing composition for a silver halide photographic light-sensitive material as described in 1 above, which contains a compound represented by the general formula [I].

10. 3. The color developing solution for a silver halide photographic light-sensitive material as described in 2 above, which contains the compound represented by the general formula [I].

11. 4. The bleaching solution for silver halide photographic light-sensitive materials as described in 3 above, which contains the compound represented by the general formula [I].

12. 5. The bleach-fixing solution for silver halide photographic light-sensitive materials as described in 4 above, which contains the compound represented by the general formula [I].

That is, as a result of various studies, the present inventor has conducted a processing composition for a silver halide photographic light-sensitive material, a color developing solution, a bleaching solution, a bleach-fixing solution, a stabilizing solution, a fixing solution, an amplifier solution or black-and-white developing. When at least one selected from the liquids contains the compound represented by the general formula [A], the effects of the present invention are exhibited, and a processing agent composition for a silver halide photographic light-sensitive material, a color developer, It was found that the effect of the present invention can be further exhibited by further containing the compound represented by the general formula [I] in at least one selected from the bleaching solution and the bleach-fixing solution, and the present invention was achieved.

The present invention will be described in detail below. In the general formula [A], R represents a hydrogen atom or a hydroxyl group,
A _{1 to} A ₄ are each —CH ₂ OH, —COOM ₁ or —PO _3.
M ₂ M ₃ is represented, and each of M _{1 to} M ₃ is a hydrogen atom, an alkali metal (eg, sodium, potassium) or another cation (eg, ammonium ion, methylammonium ion, trimethylammonium ion, etc.). n represents an integer of 1 or 2.

Specific compounds represented by the general formula [A] are shown below, but the present invention is not limited thereto.

[0034]

[Chemical 3]

These compounds can be synthesized by a generally known method. Optical isomers are preferably used, and a particularly preferable compound is (A-1).

In the above general formula [I], A ^{1 to} A ⁴ may be the same or different, and --CH ₂ O
Represents H, -COOM ³ or -PO ₃ M ¹ M ^2. M ¹ , M ² and M ³ each represent a hydrogen atom, an alkali metal (eg sodium, potassium) or another cation (eg ammonium ion, methylammonium ion, trimethylammonium ion etc.). X is (including substituted derivatives) alkylene group having 2 to 6 carbon atoms or ^{- (B 1 O) n-} B 2 -
Represents B ¹ and B ² each represent an alkylene group having 1 to 5 carbon atoms (including a substituted product).

Examples of the alkylene group represented by X include ethylene, trimethylene and tetramethylene groups.

Examples of the alkylene group represented by B ¹ and B ² include methylene, ethylene and trimethylene groups.

Examples of the substituent of the alkylene group represented by X, B ¹ or B ² include a hydroxyl group and an alkyl group having 1 to 3 carbon atoms (eg, methyl group, ethyl group, etc.). n is 1
It represents an integer of 8, and is preferably 1 to 4. Especially preferably, it is 1-2.

Preferred specific examples of the compound represented by the general formula [I] are shown below, but the invention is not limited thereto.

[0041]

[Chemical 4]

[0042]

[Chemical 5]

These compounds can be synthesized by a generally known method. Optical isomers are preferably used, and particularly preferred compounds are (I-1) and (I-
2) and (I-7).

The amount of the compound represented by the general formula [A] or the general formula [I] to be blended in the photographic processing composition is preferably 0.1 to 50 g, more preferably 1 to 50 g, per 1 L of the finishing processing liquid. It is 0.5 to 10 g. At the time of blending, two or more compounds represented by the above general formulas [A] and [I] may be used in combination, or may be used in combination with another chelating agent. When preparing the treatment liquid, the treatment liquid may be added to the treatment liquid together with other components, or may be added to the kit together with other components in a powder form or in the concentrated liquid kit. Good.

The photographic processing composition of the present invention can be applied to any processing solution for processing a silver halide photographic light-sensitive material. For example, general black and white developing solution, first developing solution for reversal film, squirrel infectious developing solution, color developing solution, bleaching solution, fixing solution, bleach-fixing solution, stopping solution, hardening solution, stabilizing solution, amplification. Examples thereof include, but are not limited to, an ar solution, a fog solution, and a toning solution. Further, the photographic processing composition of the present invention is used for all silver halide photographic light-sensitive materials such as color film, color photographic paper, reversal film, general-purpose black and white film, X-ray film, printing lith film and micro film. Can be used for processing.

[0046]

The present invention will be described in more detail with reference to the following examples, but the embodiments of the present invention are not limited thereto.

Example 1 A color photographic paper developer having the following composition was prepared as a photographic processing composition.

Potassium carbonate 30 g Potassium bromide 5 mg Potassium chloride 1.2 g Triethanolamine 15 g Diethylene glycol 10 g Potassium sulfite 0.5 g Hydroxylamine sulfate 0.5 g Disulfoethylhydroxylamine 5 g Benzyl alcohol 2 g 3-Methyl-4-amino- N-ethyl-N- (β-methanesulfonamidoethyl) aniline sulfate 6.0 g Potassium hydroxide 1.4 g Optical brightener (Tinopearl SFP) 2 g Water to 1 L, potassium hydroxide and 20% sulfuric acid The pH was adjusted to 10.2.

Sample (1-1) was prepared by adding the above exemplified compound (A-1) to the above developing solution at a rate of 2 g / L. Similarly, the exemplified compound (A-
7) 2 g / L was added to the sample (1-3), and sodium hexametaphosphate (hereinafter abbreviated as HMP) was 2 g / L.
Sample (1-4) was added, and 3.3 g / L of a 60% solution of 1-hydroxyethylidene-1,1-diphosphonic acid (hereinafter abbreviated as HEDP) was added to sample (1-).
5), a sample (1-6) to which 2 g / L of ethylenediaminetetraacetic acid (hereinafter abbreviated as EDTA) was added and a sample (1-7) to which 2 g / L of nitrilotriacetic acid (hereinafter abbreviated as NTA) was added ) And seven kinds of samples were prepared.

Since the pH of each sample varies depending on the substance added, the pH was adjusted to 10.2 using potassium hydroxide or dilute sulfuric acid, and the following experiments were conducted.

(Experiment 1) 1.7 ppm of ferric ion and 0.4 ppm of copper ion were added to each of the above-mentioned developer samples (hereinafter also simply referred to as samples) (1-1) to (1-7), After left at 35 ° C. for 5 days, hydroxylamine was quantitatively analyzed to determine its reduction rate. The results are shown below.

(Experiment 2) Polyethylene was laminated on one side of a paper support and polyethylene having titanium oxide was laminated on the other side of the first layer, and each layer having the following constitution was applied to form a multilayer. A color light-sensitive material was produced. The coating liquid was prepared as follows.

First layer coating solution Yellow coupler (Y-1) 25.1 g, dye image stabilizer (ST-1) 10.0 g, (ST-2) 6.67
g, 0.67 g of stain inhibitor (HQ-1) were dissolved in 6.67 g of high boiling point solvent (DNP) by adding 60 ml of ethyl acetate, and this solution was dissolved in 7 ml of 20% surfactant (SU-1).
A yellow coupler dispersion was prepared by emulsifying and dispersing it in 220 ml of a 10% gelatin aqueous solution containing a using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 9.5 g of silver) prepared under the following conditions to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. Also, as a hardener, the second layer and the fourth layer
(H-1) was added to the layer and (H-2) was added to the seventh layer. As the coating aid, surfactants (SU-2), (SU-
3) was added to adjust the surface tension.

[0055]

[Table 1]

[0056]

[Table 2]

[0057]

[Chemical 6]

[0058]

[Chemical 7]

[0059]

[Chemical 8]

[0060]

[Chemical 9]

[Preparation of blue-sensitive silver halide emulsion] 40 ° C.
The following (solution A) and (solution B) were added to 1000 ml of a 2% aqueous gelatin solution kept at pAg = 6.5 and pH = 3.0.
Controlled to 30 minutes at the same time, the following (C
Liquid) and (D liquid) were simultaneously added over 180 minutes while controlling pAg = 7.3 and pH = 5.5. At this time, pA
The g was controlled by the method described in JP-A-59-45437, and the pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Liquid A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Liquid B) Silver nitrate 10 g Water was added to 200 ml (Liquid C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water 600 ml (D liquid) 300 g of silver nitrate 300 g of water is added, and after the addition of 600 ml is completed, desalting is performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution. And average particle size 0.85μ
m, coefficient of variation (σ / r) = 0.07, silver chloride content 9
9.6 mol% of monodisperse cubic emulsion EMP-1 was obtained.

The emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer (STAB-1) 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye (BS-1) 4 × 10 ⁻⁴ Mol / mole AgX sensitizing dye (BS-2) 1 × 10 ⁻⁴ mol / mole AgX [Preparation of green-sensitive silver halide emulsion] (solution A) and (solution B)
The average particle size is 0.43 μm in the same manner as EMP-1 except that the addition time of (C liquid) and the addition time of (C liquid) are changed.
m, coefficient of variation (σ / r) = 0.08, silver chloride content 9
9.6 mol% of monodisperse cubic emulsion EMP-2 was obtained.

For EMP-2, the following compounds were used:
Chemical ripening was carried out at 5 ° C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer (STAB-1) 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye (GS-1) 4 × 10 ⁻⁴ Mol / mol AgX [Preparation of red-sensitive silver halide emulsion] (solution A) and solution B
0.50μ in average particle size in the same manner as EMP-1 except that the addition time of (C liquid) and the addition time of (D liquid) are changed.
m, coefficient of variation (σ / r) = 0.08, silver chloride content 9
A 9.7 mol% monodisperse cubic emulsion EMP-3 was obtained.

The following compounds were used for EMP-3:
Chemical ripening was performed at 0 ° C. for 90 minutes to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer (STAB-1) 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye (RS-1) 4 × 10 ⁻⁴ Mol / mol AgX

[0069]

[Chemical 10]

The color photographic papers produced as described above were subjected to white stepwise exposure using a sensitometer, and then left for 7 days in Experiment 1 to obtain developer samples (1-1) to (1-7). )
Was used according to the following steps.

[0071] (Composition of bleach-fix solution) Ethylenediaminetetraacetic acid 4g Ammonium sulfite (50% solution) 30ml Ammonium thiosulfate (70% solution) 140ml Ammonia water (28% solution) 30ml Ethylenediaminetetraacetic acid ferric sodium 70g Water is added to make 1L. It was

With respect to the products which have undergone the above color development processing,
The fog density of the unexposed blue reflection density was measured using a PDA65 type photoelectric densitometer (manufactured by Konica Corporation).

(Experiment 3) Developer samples (1-1) to (1-
To 7), 220 ppm of calcium ion and 3200 ppm of sodium ion were added, and the mixture was allowed to stand at room temperature for 7 days to observe the occurrence of precipitation.

The results of Experiments 1 to 3 are summarized in Table 3.

[0075]

[Table 3]

As shown by the results in Table 3, the samples (1-2) and (1-3) of the present invention showed less decomposition of hydroxylamine, less fog, and no precipitation due to the presence of metal ions. I understand. On the other hand, a comparative sample (1-
In 5), although it is effective in suppressing the decomposition of hydroxylamine and generating fog to some extent, it is not effective at all in generating precipitation due to the presence of metal ions and cannot be used. Further, the comparative sample (1-6) has the same effect on the occurrence of precipitation as the chelating agent used in the present invention, but promotes the decomposition of hydroxylamine and causes remarkable fog, and cannot be used. Samples (1-1), (1-4)
Also, (1-7) is not suitable for practical use because it decomposes hydroxylamine and causes fog, and the ability to prevent precipitation due to the presence of metal ions is weak.

Example 2 A first developing solution (black and white developing solution) for reversal films having the following composition was prepared as a photographic processing composition.

[0078]   55 ml of potassium sulfite (50% solution)   2.2 g of sodium bromide   Sodium thiocyanate 1.0g   Solubilized potassium 3mg   20 ml of diethylene glycol   1-phenyl-3-pyrazolidone (trade name phenidone) 0.60 g   Hydroquinone 6.0g   28.2 g of potassium carbonate   2.8g potassium hydroxide Add water to make 1 liter.

The above developer was used as a sample (2-1), and ethylenediaminetetraacetic acid (hereinafter abbreviated as EDTA) was added to the sample (2-1).
The sample (2-2) was added at a ratio of g / L. Similarly, a sample (2-3) was prepared by adding Exemplified Compound A-1 at a rate of 2 g / L, and a sample (2-3) was prepared by adding 2 g / L of ethylenediaminetetramethylenephosphonic acid (hereinafter abbreviated as EDTP). 4) and three kinds of samples in total were prepared. Each sample was adjusted to have a pH of 9.90 using potassium hydroxide or 20% sulfuric acid.

Ferric ions of 2.0 p were added to each of the above samples.
Add 200 ppm of pm and calcium ion,
After left at 5 ° C for 5 days, quantitative analysis was performed to measure the reduction rate of phenidone, and the occurrence of precipitation was visually observed. The results obtained are shown in Table 4.

[0081]

[Table 4]

As shown in the results of Table 4, the comparison sample (2
-2) effectively prevents the occurrence of precipitation due to the presence of metal ions, but accelerates the decomposition of phenidone which is a developing agent. On the other hand, the comparative samples (2-1) and (2-4) have little or no effect on the decomposition of phenidone, and have little effect on the prevention of precipitation. On the contrary, it can be seen that the sample (2-3) containing the chelating agent of the present invention effectively prevents the occurrence of precipitation and also effectively suppresses the decomposition of phenidone.

Example 3 As a photographic processing composition, a bleaching solution (1) having the following composition,
Two types of (2), a fixing solution and a bleach-fixing solution were prepared, and the effects of the exemplified compounds on the occurrence of precipitation due to metal ions were tested for both solutions.

[0084]   Bleach (1)   Ethylenediaminetetraacetic acid ferric ammonium salt (dihydrate) 125g   Ammonium bromide 98g Add water to make 1 liter.

[0085]   Bleach (2)   1,3-Diaminopropanetetraacetic acid ferric ammonium 140g   40 g of sodium nitrate   Ammonium bromide 150g   Glacial acetic acid 45g Add water to make 1 liter.

[0086]   Fixer   Ammonium thiosulfate 200g   Ammonium sulfite 25g   Potassium metabisulfite 8g Add water to make 1 liter.

[0087]   Bleach-fix solution   Ethylenediaminetetraacetic acid ferric ammonium 65g   20 ml of ammonium sulfite (40% solution)   Ammonium thiosulfate (70% solution) 250 ml   Ammonia water (28% solution) 30 ml Add water to make 1 liter.

The above two types of bleaching solutions (1) and (2), the fixing solution and the bleach-fixing solution were used as they were for comparison, and the exemplified compounds (A-2), (A-7) and (A) were used. −
16) were prepared by adding 9) at a rate of 4 g / L each. Aqueous ammonia or acetic acid is used for these solutions, and the bleaching solution (1) has a pH of 6.0 and the bleaching solution (2).
For pH 4.2, for fixer pH 6.8,
The bleach-fix solution was adjusted to pH 7.1, and 600 ppm of calcium ion was added to each solution.

When this was left to stand, the comparative one, to which nothing was added, showed remarkable precipitation in both the fixer and the bleach-fixer, but the sample to which the compound of the present invention was added produced only a slight precipitate. It was

Example 4 As a photographic processing composition, a stabilizing solution having the following composition was prepared, 5% of the bleach-fixing solution used in Example 3 was added, and the effect of preventing the formation of floating substances due to sulfurization was tested.

Stabilizing liquid 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g diethylene glycol 1.0 g 2-octyl-4-isothiazolin-3 -On 0.01 g Benzotriazole 1 g Ammonia water (28%) 3 ml Water was added to make 1 L, and the pH was adjusted to 8.0 with potassium hydroxide and 20% sulfuric acid.

The above stabilizers were used as they were for comparison, and the exemplified compounds (A-2), (A-7) and (A-
Three kinds of samples of the present invention were prepared by adding 9) at a rate of 3 g / L.

These stabilizing solutions were adjusted to pH 8.0 with KOH or 20% sulfuric acid, and 100 ppm of calcium ion was added to each solution and allowed to stand. As a result, in the case of the comparative sample to which nothing was added, precipitation occurred and a floating substance was generated on the surface in 2 days, but the exemplary compound (A-2),
The samples of the present invention to which (A-7) and (A-9) are added are 10
No abnormality was observed even after a day. Furthermore, the effect was recognized also about the generation of mold.

Example 5 Chelating agents commonly known for use in photography, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), N-hydroxyethylethylenediaminetriacetic acid (HEDTA), exemplified compounds ( For A-1) and (A-7), 301C modified MITI test (I) in the OECD test guideline for chemicals
(Adopted May 12, 1981), the degree of biodegradation was determined. At this time, the degree of biodegradation of the exemplified compound (A-1) was 100.
Table 5 shows the results when the relative degree of decomposition was calculated.

[0095]

[Table 5]

From Table 5, the chelating agent of the present invention has extremely good biodegradability and shows that it has EDTA, DTPA and HEDT.
Compared with A, it can be seen that it is extremely preferable from the standpoint of global environment protection.

Example 6 30 ml of hydrogen peroxide (35% solution), sodium carbonate (15 g) and 6-aminopurine (20 mg) were dissolved in 1 L of water, and the pH was adjusted to 1 with diluted sulfuric acid or potassium hydroxide.
Amplifier liquid (6-
Used as 1).

In this amplifier liquid (6-1),
Various chelating agents (1 g / L) described in Table 6 were added, and p
H was adjusted so as to maintain 10.0, and amplifier solutions (6-2) to (6-7) were produced.

Ferric ion 2 was added to each amplifier liquid.
ppm, calcium ion 150 ppm and sodium ion 500 ppm were added and left at 35 ° C. for 6 days,
The hydrogen peroxide concentration after storage was measured to determine the residual rate (Experiment 4), and the state of precipitation was visually observed (Experiment 5). The details of the amplifier liquid (also referred to as the reinforcing liquid) are described in JP-B-63-33139.

Table 6 shows the above results.

[0101]

[Table 6]

From Table 6, it can be seen that when the compound of the present invention is used in the amplifier liquid, the residual amount of hydrogen peroxide is large and the precipitation is small as compared with the case where other chelating agents are used. I understand.

Example 7 An experiment was conducted in the same manner as in Example 1 except that 1 g / L of each of Compounds I-1 and I-3 was added to the developer sample (1-3) of Example 1. . Furthermore, the developer sample (1
In -3), 1 g / L of EDTA or NTA was added and the same experiment as above was performed.

As a result, when the compound represented by the general formula [A] is used in combination with the compound represented by the general formula [I], the reduction ratio of hydroxylamine is 3 to 3, respectively.
It was improved by 5% and the fog density was improved by 10 to 15%.
However, when the compound represented by the general formula [A] was used in combination with EDTA or NTA, the reduction rate of hydroxylamine was hardly improved, and the fog density was not improved.

Example 8 To the bleaching solution (2) and the bleach-fixing solution of Example 3, 4 g / L of Exemplified Compound (A-1) and 1 g / L of Compound I-1 or I-3 were added, respectively. Others were the same as in Example 3, and the experiment was performed. As a result, no precipitation occurred at all, and the sulfidation rate was improved 1.7 times. But,
This effect was not exhibited even when comparative EDTA or NTA was added instead of the compound represented by the general formula [I].

[0106]

When the photographic processing composition, color developing solution, bleaching solution, bleach-fixing solution, stabilizing solution, fixing solution, amplifier solution and black-and-white developing solution of the present invention are used, the following excellent properties are obtained. There is an effect. (1) There is no oxidation or decomposition of the active ingredient in the treatment liquid due to the action of metal ions, the efficacy of the treatment liquid is maintained for a long time, and a constant treatment result is always obtained. (2) Even if metal ions are present or mixed in the processing liquid, neither precipitation nor sludge is generated, and the filter is not clogged and the photographic light-sensitive material which is the object to be processed is not contaminated. (3) It has extremely good biodegradability and is preferable in terms of protecting the global environment.

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Claims (12)

[Claims] 1. A processing composition for a silver halide photographic light-sensitive material, which contains a compound represented by the following general formula [A]. [Chemical 1] [In the formula, R represents a hydrogen atom or a hydroxyl group, A _{1 to} A ₄ each represent —CH ₂ OH, —COOM ₁ or —PO ₃ M ₂ M _3, and each of M _{1 to} M ₃ represents a hydrogen atom or an alkali. Represents a metal or other cation. n represents an integer of 1 or 2. ] 2. A color developing solution for a silver halide photographic light-sensitive material, which contains a compound represented by the general formula [A]. 3. A bleaching solution for a silver halide photographic light-sensitive material, which contains a compound represented by the general formula [A]. 4. A bleach-fixing solution for silver halide photographic light-sensitive materials, which contains the compound represented by the general formula [A]. 5. A stabilizer for a silver halide photographic light-sensitive material, which contains a compound represented by the general formula [A]. 6. A fixing solution for a silver halide photographic light-sensitive material, comprising a compound represented by the general formula [A]. 7. An amplifier liquid for a silver halide photographic light-sensitive material, containing the compound represented by the general formula [A]. 8. A black and white developing solution for a silver halide photographic light-sensitive material, which contains the compound represented by the general formula [A]. 9. The processing composition for a silver halide photographic light-sensitive material according to claim 1, which contains a compound represented by the following general formula [I]. [Chemical 2] [In the formula, A ¹ , A ² , A ³ and A ⁴ are each —CH ₂ OH, —
Represents COOM ³ or —PO ₃ M ¹ M ² , M ¹ , M ² and M ³
Each represents a hydrogen atom, an alkali metal or another cation. X is an alkylene group having 2 to 6 carbon atoms or-(B
¹ O) represents n-B ^2- . n represents an integer of 1 to 8, and B ¹ and B ² each represent an alkylene group having 1 to 5 carbon atoms. ] 10. The color developing solution for silver halide photographic light-sensitive materials according to claim 2, which contains the compound represented by the general formula [I]. 11. The bleaching solution for a silver halide photographic light-sensitive material according to claim 3, which contains the compound represented by the general formula [I]. 12. The bleach-fixing solution for silver halide photographic light-sensitive materials according to claim 4, which contains the compound represented by the general formula [I].